Synthesis of sulfonate ester and sulfonic acid-containing poly(arylene perfluorocyclobutane)s (PFCB) by direct copolymerization of a sulfonate ester-containing precursor

• Published in: Polymer (Guilford) Vol. 108; pp. 179 - 192
• Main Authors: Marestin, Catherine, Thiry, Xavier, Rojo, Sergio, Chauveau, Edouard, Mercier, Regis
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 13.01.2017; Elsevier BV; Elsevier
• Subjects: Biphenyl; Chemical properties; Chemical Sciences; Chemical synthesis; Copolymerization; Copolymers; Esters; Hydrolysis; Material chemistry; Monomers; Physicochemical properties; Polymerization; Polymers; Precursors; Sulfonate ester bistrifluorovinyl ether; Sulfonated poly(arylene perfluorocyclobutane); Sulfonates; Sulfonic acid; Sulfuric acid; Synthesis (chemistry); Sulfonate ester bistrifluorovinyl ether; Sulfonated poly(arylene perfluorocyclobutane)
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2016.11.061

This paper reports the first synthesis of sulfonated poly(arylene perfluorocyclobutane)s by direct polycondensation of a new sulfonate ester-containing bis(trifluorovinylether) precursor and subsequent hydrolysis of the resulting polymers. The multi-step synthesis of a bis(trifluorovinylether) monomer bearing sulfonic acid groups protected as sulfonate esters (SE-TFVE) is described. Based on this precursor and 4,4′-bis(trifluorovinyloxy)biphenyl (4,4′-TFVE), sulfonate ester-containing poly(arylene perfluorocyclobutane) copolymers (SE-PFCB) were synthesized by 2π + 2π step-growth cyclopolymerization. Their thermal and physico-chemical properties were characterized. Free acid polymers (SA-PFCB) were subsequently obtained by hydrolysis of sulfonate ester groups. A preliminary evaluation of the proton conductive properties of these polymers is reported. [Display omitted] •Sulfonate ester-containing bistrifluorovinyl ether monomer synthesis.•Direct polycondensation of sulfonate ester-containing precursor.•Synthesis and characterization of sulfonated Poly(arylene perfluorocyclobutane)s.